Divergent [2 + n ] Heteroannulation of β-CF 3 -1,3-enynes with Alkyl Azides via Hydrogen Atom Transfer and Radical Substitution

作者：Yuzhong Yang, Qi Xue, Zhiqiang Xiong, Yang Li, Xuan‐Hui Ouyang, Ming Hu, Jin‐Heng Li · 发表于：Organic Letters · 年份：2024 · DOI：10.1021/acs.orglett.3c04041 · 被引用次数：10 · 研究领域：Fluorine in Organic Chemistry、Catalytic C–H Functionalization Methods、Synthesis and Catalytic Reactions

A copper-promoted divergent intermolecular [2 + n ] heteroannulation of β-CF 3 -1,3-enynes with alkyl azides via alkyl radical-driven HAT and radical substitution (C–C bond formation) to form four- to ten-membered saturated N -heterocycles is developed. This method enables the aryl-induced or kinetically controlled site selective functionalization of the remote C(sp 3 )–H bonds at positions 2, 3, 4, 5, 6, 7, or 8 toward the nitrogen atom through triplet nitrene formation, radical addition across the C═C bond, HAT and radical substitution cascades, and features a broad substrate scope, excellent site selectivity, and facile late-stage derivatization of bioactive molecules. Initial deuterium-labeling and control experiments shed light on the reaction mechanism via nitrene formation and HAT.